US3978089A - Caryophyllane epoxide - Google Patents

Caryophyllane epoxide Download PDF

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US3978089A
US3978089A US05/378,478 US37847873A US3978089A US 3978089 A US3978089 A US 3978089A US 37847873 A US37847873 A US 37847873A US 3978089 A US3978089 A US 3978089A
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caryophyllane
epoxide
formula
oil
norcaryophyll
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US05/378,478
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Roman Kaiser
Dietmar Lamparsky
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Givaudan Roure Corp
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Givaudan Corp
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Priority claimed from CH1084372A external-priority patent/CH579086A5/en
Priority claimed from CH1084472A external-priority patent/CH567418A5/en
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Assigned to GIVAUDAN CORPORATION reassignment GIVAUDAN CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 12/19/1991 NEW JERSEY Assignors: ROURE, INC. (MERGED INTO)
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common

Definitions

  • This invention relates to the field of odorants.
  • the present invention relates to caryophyllane derivatives. More particularly, the invention is concerned with caryophyllane derivatives and a process for the manufacture thereof. The invention is also concerned with odorant compositions containing said caryophyllane derivatives and with a method of imparting an odour to products by means of said derivatives.
  • R 1 and R 2 together represent an oxo group and R 3 and R 4 together represent a C--C bond or R 1 represents a methyl group, R 2 and R 4 together represent an epoxide group and R 3 represents a hydrogen atom.
  • this invention is concerned, in one of its aspects, with the novel 12-norcaryophyll-6-en-3-one and the hitherto unknown 3,7-caryophyllane epoxide insofar as it is synthetically manufactured as well as with 3,7-caryophyllane epoxide in substantially pure form or in admixture with other odorants and/or solvents or carriers, with the exception of verbena oil.
  • Caryophyllene occurs widely in nature in essential oils, primarily in clove oil (Eugenia caryophyllata) from which it can be isolated in admixture with about 10% humulene. Pure caryophyllene can readily be produced from commercial caryophyllene by column chromatography on Kieselgel.
  • the hitherto unknown 3,7-caryophyllane epoxide of formula Ib has been found in small amounts in verbena oil from which it can be isolated in accordance with known methods, preferably by distillation and chromatography.
  • 3,7-Caryophyllane epoxide of formula Ib itself has a woody, balsamic odour.
  • 3,7-caryophyllane epoxide to many odorant compositions imparts thereto more depth and tenacity.
  • it has a strong modifying action in combination with individual odorants (e.g. citral).
  • This epoxide can accordingly be used, with advantage, for imparting a bouquet to citral and citral-like odorants such as occur, amongst others, in verbena oil.
  • odorant compositions such as perfumes or for perfuming technical or cosmetic products of all kinds such as, for example, solid or liquid detergents, synthetic washing agents, aerosols, soaps, lotions, creams etc.
  • the content of 3,7-caryophyllane epoxide in odorant compositions or in perfumed products can vary within wide limits.
  • perfume compositions it can be present in an amount of between about 0.01 and 20 wt %, preferably between 2 and 10 wt %, and in finished products such as soaps, lotions, creams it can preferably be present in an amount of between 0.01 and 0.5 wt %.
  • 12-Norcaryophyll-6-en-3-one of formula Ia likewise possesses particular fragrance qualities. It possesses a woody, somewhat earthy fragrance partially reminiscent of sandal or vetiver.
  • 12-norcaryophyll-6-en-3-one to odorant compositions imparts thereto a warmer and fuller odour.
  • 12-Norcaryophyll-6-en-3-one blends especially well with woody smelling compositions and essential oils. It can accordingly be used as an odorant in the perfume industry; for example for the manufacture of, or for modifying the odour of, odorant compositions such as perfumes, perfume bases etc, by the addition of olfactory perceptible amounts (e.g.
  • 12-Norcaryophyll-6-en-3-one can also be used for the perfuming of technical and cosmetic products of all kinds; for example solid and liquid detergents, synthetic washing agents, aerosols, soaps, creams, lotions etc in concentrations of, for example, about 0.02-0.1 wt %.
  • the reductive elimination of the 6,7-epoxy group of 6,7-epoxy-12-norcaryophyllan-3-one of formula III according to embodiment (a) of the process can be carried out in a manner known per se; for example, by treatment with a chromium (II)-ethylenediamine complex [I. K. Kochi et al., Tetrahedron 24, 3503 (1968)] or by means of weakly coppered zinc in boiling ethanol [S. M. Kupchan and M. Marnyama, J. Org. Chem. 36, 1187 (1971)].
  • a chromium (II)-ethylenediamine complex I. K. Kochi et al., Tetrahedron 24, 3503 (1968)
  • weakly coppered zinc in boiling ethanol S. M. Kupchan and M. Marnyama, J. Org. Chem. 36, 1187 (1971)].
  • the cyclization of caryophyll-6-en-3-ol according to embodiment (b) of the process can also be carried out in a manner known per se by treatment with an acid catalyst such as an inorganic acid, a Lewis acid or an organic sulphonic acid (e.g. p-toluenesulphonic acid, boron trifluoride etherate or a 1:1 mixture of boron trifluoride and phosphoric acid) in one of the usual inert organic solvents such as dioxane, diethyl ether, benzene, toluene etc.
  • the treatment can be carried out within a wide temperature range, preferably at between 0°C and the reflux temperature of the mixture.
  • 6,7-epoxycaryophyllene of formula V into 6,7-epoxy-12-norcaryophyllan-3-one of formula III can be carried out, for example, by ozonolysis of the exocyclic double-bond or by oxidation with permanganate, while the selective epoxidation of the endocyclic double-bond of caryophyllene can be carried out by means of a peracid (e.g. peracetic acid) in a suitable solvent (e.g. methylene chloride) and in the presence of sodium acetate.
  • a peracid e.g. peracetic acid
  • a suitable solvent e.g. methylene chloride
  • 12-Norcaryophyll-6-en-3-one of formula Ia can be converted by reaction with a GRIGNARD compound of the formula H 3 C--Mg--Hal (in which Hal stands for a chlorine, bromine or iodine atom) in a known manner into caryophyll-6-en-3-ol of formula IV which is used as the starting material for embodiment (b) of the process.
  • a GRIGNARD compound of the formula H 3 C--Mg--Hal in which Hal stands for a chlorine, bromine or iodine atom
  • IR: ⁇ max 2930, 2858, 1695, 1450, 1381, 1369, 1351, 1331, 1279, 1225, 1160, 1113, 1090, 1059, 1018, 990 and 811 cm.sup. -1 .
  • the compound has a woody, slightly camphoraceous odour reminiscent of sandal, vetiver and cedar.
  • IR: ⁇ max 2930, 2860, 1460, 1370, 1281, 1231, 1210, 1180, 1117, 1099, 1075, 1058, 989, 969, 900, 840 and 815 cm.sup. -1 .
  • the starting material can be prepared as follows:
  • IR: ⁇ max 3490, 2920, 2856, 1670, 1450, 1380, 1366, 1280, 1274, 1199, 1105, 1080, 1052, 990, 939, 890, 871, 855, 820 and 800 cm.sup. -1 .
  • the compound has a woody, earthy, patchouli-type odour.
  • the composition has a pronounced woody-spicy character and is suitable for the perfuming of male cosmetics.
  • composition has a fantasy-floral note which is especially suitable for the perfuming of soap.
  • the composition is given more tenacity and depth.
  • the base acts somewhat woody and warmer.

Abstract

Novel caryophyllane derivatives, a process for their manufacture and odorant compositions containing the novel compounds are disclosed.

Description

FIELD OF THE INVENTION
This invention relates to the field of odorants.
SUMMARY OF THE INVENTION
The present invention relates to caryophyllane derivatives. More particularly, the invention is concerned with caryophyllane derivatives and a process for the manufacture thereof. The invention is also concerned with odorant compositions containing said caryophyllane derivatives and with a method of imparting an odour to products by means of said derivatives.
The caryophyllane derivatives with which the present invention is concerned have the following general formula ##SPC1##
Wherein R1 and R2 together represent an oxo group and R3 and R4 together represent a C--C bond or R1 represents a methyl group, R2 and R4 together represent an epoxide group and R3 represents a hydrogen atom.
It will be appreciated that formula I hereinbefore embraces 12-norcaryophyll-6-en-3-one of the formula ##SPC2##
And 3,7-caryophyllane epoxide of the formula ##SPC3##
Thus, this invention is concerned, in one of its aspects, with the novel 12-norcaryophyll-6-en-3-one and the hitherto unknown 3,7-caryophyllane epoxide insofar as it is synthetically manufactured as well as with 3,7-caryophyllane epoxide in substantially pure form or in admixture with other odorants and/or solvents or carriers, with the exception of verbena oil.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The fundamental substance from which the compounds of formula I are derived is caryophyllene of the formula ##SPC4##
Caryophyllene occurs widely in nature in essential oils, primarily in clove oil (Eugenia caryophyllata) from which it can be isolated in admixture with about 10% humulene. Pure caryophyllene can readily be produced from commercial caryophyllene by column chromatography on Kieselgel.
The hitherto unknown 3,7-caryophyllane epoxide of formula Ib has been found in small amounts in verbena oil from which it can be isolated in accordance with known methods, preferably by distillation and chromatography.
Natural verbena oil is obtained by steam distillation from Lippia citriodora Kunth. (= Verbena triphylla l'Herit = Aloysia citriodora Ort.) which is indigenous to South America and which is principally cultivated there. Natural verbena oil is very valuable in the perfume industry because of its fine lemon-like odour with a balsamic foundation. It is, however, very expensive and relatively difficult to obtain commercially, this being related to the special climatic conditions which are a prerequisite for the cultivation of the plants. On the other hand, verbena oil with a favourable price structure can be widely used in all fields of the perfume industry, especially in eaux de Cologne.
3,7-Caryophyllane epoxide of formula Ib itself has a woody, balsamic odour. As has been found, the addition of 3,7-caryophyllane epoxide to many odorant compositions imparts thereto more depth and tenacity. Also, it has a strong modifying action in combination with individual odorants (e.g. citral). This epoxide can accordingly be used, with advantage, for imparting a bouquet to citral and citral-like odorants such as occur, amongst others, in verbena oil. It can, moreover, be quite generally used as an odorant for the manufacture of odorant compositions such as perfumes or for perfuming technical or cosmetic products of all kinds such as, for example, solid or liquid detergents, synthetic washing agents, aerosols, soaps, lotions, creams etc.
The content of 3,7-caryophyllane epoxide in odorant compositions or in perfumed products can vary within wide limits. In perfume compositions it can be present in an amount of between about 0.01 and 20 wt %, preferably between 2 and 10 wt %, and in finished products such as soaps, lotions, creams it can preferably be present in an amount of between 0.01 and 0.5 wt %.
12-Norcaryophyll-6-en-3-one of formula Ia likewise possesses particular fragrance qualities. It possesses a woody, somewhat earthy fragrance partially reminiscent of sandal or vetiver. The addition of 12-norcaryophyll-6-en-3-one to odorant compositions imparts thereto a warmer and fuller odour. 12-Norcaryophyll-6-en-3-one blends especially well with woody smelling compositions and essential oils. It can accordingly be used as an odorant in the perfume industry; for example for the manufacture of, or for modifying the odour of, odorant compositions such as perfumes, perfume bases etc, by the addition of olfactory perceptible amounts (e.g. 0.1 -10 wt %) to mixtures of known odorants. One of a wide field of application is, for example, the manufacture of chypre type odorant compositions. 12-Norcaryophyll-6-en-3-one can also be used for the perfuming of technical and cosmetic products of all kinds; for example solid and liquid detergents, synthetic washing agents, aerosols, soaps, creams, lotions etc in concentrations of, for example, about 0.02-0.1 wt %.
According to the process provided by the present invention, the caryophyllane derivatives of formula I hereinbefore are manufactured by
a. reductively eliminating the 6,7-epoxy group of a 6,7-epoxy-12-norcaryophyllan-3-one of the formula ##SPC5##
to give 12-norcaryophyll-6-en-3-one of formula Ia hereinbefore, or
b. cyclizing caryophyll-6-en-3-ol of the formula ##SPC6##
with the formation of a 3,7-epoxy group to give 3,7-caryophyllane epoxide of formula Ib hereinbefore.
The reductive elimination of the 6,7-epoxy group of 6,7-epoxy-12-norcaryophyllan-3-one of formula III according to embodiment (a) of the process can be carried out in a manner known per se; for example, by treatment with a chromium (II)-ethylenediamine complex [I. K. Kochi et al., Tetrahedron 24, 3503 (1968)] or by means of weakly coppered zinc in boiling ethanol [S. M. Kupchan and M. Marnyama, J. Org. Chem. 36, 1187 (1971)].
The cyclization of caryophyll-6-en-3-ol according to embodiment (b) of the process can also be carried out in a manner known per se by treatment with an acid catalyst such as an inorganic acid, a Lewis acid or an organic sulphonic acid (e.g. p-toluenesulphonic acid, boron trifluoride etherate or a 1:1 mixture of boron trifluoride and phosphoric acid) in one of the usual inert organic solvents such as dioxane, diethyl ether, benzene, toluene etc. The treatment can be carried out within a wide temperature range, preferably at between 0°C and the reflux temperature of the mixture.
The working up of the mixture and the isolation and purification of the 3,7-caryophyllane epoxide can be carried out according to known methods. Chromatography on Kieselgel is an especially suitable purification method.
The preparation of 6,7-epoxy-12-norcaryophyllan-3-one of formula III from caryophyllene of formula II can be carried out in a manner known per se via 6,7-epoxycaryophyllene of the formula ##SPC7##
The conversion of 6,7-epoxycaryophyllene of formula V into 6,7-epoxy-12-norcaryophyllan-3-one of formula III can be carried out, for example, by ozonolysis of the exocyclic double-bond or by oxidation with permanganate, while the selective epoxidation of the endocyclic double-bond of caryophyllene can be carried out by means of a peracid (e.g. peracetic acid) in a suitable solvent (e.g. methylene chloride) and in the presence of sodium acetate.
12-Norcaryophyll-6-en-3-one of formula Ia can be converted by reaction with a GRIGNARD compound of the formula H3 C--Mg--Hal (in which Hal stands for a chlorine, bromine or iodine atom) in a known manner into caryophyll-6-en-3-ol of formula IV which is used as the starting material for embodiment (b) of the process.
The following Examples illustrate the process provided by the invention:
EXAMPLE 1
A mixture of 2.22 g of 6,7-epoxy-12-norcaryophyllan-3-one [(Kobuson), see Chem. Pharm. Bull. 17, 1390 (1969)], 88 g of weakly coppered zinc [R. D. Smith and H. B. Simmens, Org. Syn. 41, 72 (1961)] and 400 ml of ethanol is heated under reflux for 35 hours. After cooling the mixture, the precipitate is filtered off and the filtrate concentrated under reduced pressure. Chromatography of the crude product on Kieselgel yields 1.7 g of pure 12-norcaryophyll-6-en-3-one. IR: νmax = 2930, 2858, 1695, 1450, 1381, 1369, 1351, 1331, 1279, 1225, 1160, 1113, 1090, 1059, 1018, 990 and 811 cm.sup.-1. The compound has a woody, slightly camphoraceous odour reminiscent of sandal, vetiver and cedar.
EXAMPLE 2
A solution of 1.11 g of caryophyll-6-en-3-ol and 0.1 g of p-toluenesulphonic acid in 20 ml of benzene is stirred for 30 minutes at a temperature of 5°C. The mixture is then diluted with twice the amount of benzene, washed with soda solution and water, dried and concentrated under reduced pressure. Chromatography of the resulting crude product on Kieselgel yields 0.35 g (31.5%) of 3,7-caryophyllane epoxide and 0.6 g of hydrocarbon compounds. The epoxide has a woody, balsamic odour. IR: νmax = 2930, 2860, 1460, 1370, 1281, 1231, 1210, 1180, 1117, 1099, 1075, 1058, 989, 969, 900, 840 and 815 cm.sup.-1.
EXAMPLE 3
A mixture of 1.11 g of caryophyll-6-en-3-ol, 0.2 g of boron trifluoride ethyl etherate and 20 ml of ether is heated under reflux for 50 minutes. The mixture is then mixed with twice the amount of ether, washed with soda solution and water, dried and concentrated under reduced pressure. Chromatography of the resulting crude product on Kieselgel yields 0.1 g (9%) of 3,7-caryophyllane epoxide and 0.7 g of hydrocarbon compounds.
The starting material can be prepared as follows:
To a Grignard reagent prepared from 0.48 g of magnesium and 2.8 g of methyl iodide is added dropwise in the course of 5 minutes a solution of 3 g of 12-norcaryophyll-6-en-3-one in 15 ml of ether. After 15 minutes, the mixture is carefully treated, with ice cooling, with a concentrated ammonium chloride solution and then extracted with ether. The ethereal phase is washed with water, dried over sodium sulphate and concentrated. Bulb-tube distillation of the residue yields 3.05 g (94% of theory) of pure caryophyll-6-en-3-ol. IR: νmax = 3490, 2920, 2856, 1670, 1450, 1380, 1366, 1280, 1274, 1199, 1105, 1080, 1052, 990, 939, 890, 871, 855, 820 and 800 cm.sup.-1. The compound has a woody, earthy, patchouli-type odour.
The following Examples illustrate typical odorant compositions provided by this invention:
EXAMPLE A Odorant composition containing 12-norcaryophyllan-6-en-3-one 
______________________________________                                    
                  Parts by weight                                         
______________________________________                                    
γ-Methylionone                                                      
                    100                                                   
Lavandin 22/24      100                                                   
Isomethylionone     80                                                    
Amyl salicylate     50                                                    
Eugenol             50                                                    
Linalyl acetate     50                                                    
Galbanum oil 10%*   40                                                    
Iris resinoid       40                                                    
Methylnonylacetaldehyde 10%*                                              
                    40                                                    
2-Heptylcyclopentanone 10%*                                               
                    40                                                    
Petitgrain oil Paraguay                                                   
                    40                                                    
Vetiveryl acetate   40                                                    
Sauge sclaree       20                                                    
Orange oil Ital.    30                                                    
Bergamotte oil Reggio                                                     
                    30                                                    
Lemon oil Ital.     10                                                    
Terpineol           30                                                    
Geranium oil Bourbon                                                      
                    20                                                    
Musk ketone         20                                                    
Vetiver oil Bourbon 15                                                    
Ylang-Ylang oil     15                                                    
12-Norcaryophyll-6-en-3-one                                               
                    50                                                    
Sandalwood oil      30                                                    
Heliotropin         30                                                    
Coumarin            30                                                    
                    1000                                                  
______________________________________                                    
 *in phthalic acid diethyl ester
The composition has a pronounced woody-spicy character and is suitable for the perfuming of male cosmetics.
EXAMPLE B Odorant composition containing 3,7-caryophyllane epoxide 
______________________________________                                    
                      Parts by weight                                     
______________________________________                                    
Cinnamon aldehyde       100                                               
Lavender oil            100                                               
Geranium oil Bourbon    100                                               
Sandela Givaudan        100                                               
Baccartol Givaudan      60                                                
Terpineol               80                                                
para-Tertiary butyl-cyclohexyl                                            
acetate                 50                                                
Amylsalicylate          50                                                
Phenylethyl alcohol     50                                                
α-Methylionone    50                                                
Coumarin                30                                                
Musk ambrette           30                                                
Resinoid storax         50                                                
Petitgrain oil Paraguay 50                                                
Patchouli oil           20                                                
1,1,4,4-Tetramethyl-6-ethyl-7-                                            
acetyl-1,2,3,4-tetrahydronaphthalene                                      
                        30                                                
3,7-Carophyllane epoxide                                                  
                        50                                                
                        1000                                              
______________________________________
The foregoing composition has a fantasy-floral note which is especially suitable for the perfuming of soap.
By the addition of 3,7-caryophyllane epoxide, the composition is given more tenacity and depth. The base acts somewhat woody and warmer.

Claims (1)

What we claim is:
1. Substantially pure 3,7-caryophyllane epoxide.
US05/378,478 1972-07-19 1973-07-12 Caryophyllane epoxide Expired - Lifetime US3978089A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH10843/72 1972-07-19
CH1084372A CH579086A5 (en) 1972-07-19 1972-07-19 Caryophyllene derivs - useful as perfume ingredients
CH1084472A CH567418A5 (en) 1972-07-19 1972-07-19 Caryophyllene derivs - useful as perfume ingredients
CH10844/72 1972-07-19

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US3978089A true US3978089A (en) 1976-08-31

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US (1) US3978089A (en)
JP (1) JPS4951256A (en)
DE (1) DE2335046A1 (en)
FR (2) FR2194678B1 (en)
GB (1) GB1377355A (en)
NL (1) NL7309554A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115256A1 (en) * 2004-12-01 2006-06-01 Pentax Corporation Imaging device having an optical image stabilizer
US20110028542A1 (en) * 2007-05-31 2011-02-03 Jean Legault Compositions for prevention or treatment of anorexia-cachexia syndrome and uses thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
naves et al., Chem. Abstracts, vol. 55, entry 11766e (1961).
naves et al., Chem. Abstracts, vol. 55, entry 11766e (1961). *
Nigam et al., Chem. Abstracts, vol. 62, entry 14731e at f (1965). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115256A1 (en) * 2004-12-01 2006-06-01 Pentax Corporation Imaging device having an optical image stabilizer
US20110028542A1 (en) * 2007-05-31 2011-02-03 Jean Legault Compositions for prevention or treatment of anorexia-cachexia syndrome and uses thereof

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FR2194678B1 (en) 1978-02-17
GB1377355A (en) 1974-12-11
NL7309554A (en) 1974-01-22
DE2335046A1 (en) 1974-01-31
JPS4951256A (en) 1974-05-18
FR2205512B1 (en) 1976-11-26
FR2205512A1 (en) 1974-05-31
FR2194678A1 (en) 1974-03-01

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